Glass fiber sizing compositions, sized glass fibers, and polyolefin composites

ABSTRACT

The present invention relates to sizing compositions, to glass fibers at least partially coated with such sizing compositions, to a variety of fiber glass products at least partially coated with such sizing compositions, and to composites formed from cycloolefins and reinforced with glass fibers at least partially coated with sizing compositions of the present invention. In one non-limiting embodiment, a sizing composition for glass fibers comprises a film-former comprising a polymer, wherein the repeating unit of the polymer comprises at least four carbon atoms and at least one carbon-carbon double bond, and a silane. A sizing composition for glass fibers, in another non-limiting embodiment, comprises a film-former comprising a polymer, wherein the repeating unit of the polymer comprises four to six carbon atoms and one carbon-carbon double bond, in an amount between about 60 and about 90 weight percent on a total solids basis, and a silane comprising a terminal vinyl group in an amount between about 5 and about 25 weight percent on a total solids basis.

FIELD OF THE INVENTION

The present invention relates generally to sizing compositions for glassfibers and, in particular, to sizing compositions for glass fiberssuitable to reinforce polyolefin articles, including dicyclopentadiene(DCPD) resins.

BACKGROUND OF THE INVENTION

Glass fibers are produced by flowing molten glass via gravity through amultitude of small openings in a precious metal device, called abushing. Typical formulations of glass fibers are disclosed in K.Loewenstein, The Manufacturing Technology of Continuous Glass Fibres,(3d Ed. 1993).

After the fibers have cooled very shortly after their issuance from thebushing and usually in close proximity to the bushing, these fibers aretreated with a chemical treating formulation usually referred to in theart as a sizing composition, sizing, or size. The sizing compositionserves to make the fibers more compatible with the material they willultimately be used to reinforce and to make the fibers easier toprocess. The sizing composition can be applied by sprayers, rollers,belts, metering devices or any similar application device. The sizedglass fibers are gathered into bundles or strands comprising a pluralityof individual fibers, generally from 200 to more than 4000.

After their formation and treatment, the strands can be wound into aspool or “forming package” and/or may be chopped. The forming packagesor chopped strands are usually dried in either an oven or at roomtemperature to remove some of the moisture from the fibers. Strands fromthe forming packages may also be wound into rovings.

The strands of treated fibers can be used to reinforce various materialssuch as thermoplastic polymers and thermosetting polymers. One exampleof a commercially important use of treated fibers is to reinforceolefinic thermosetting polymers, especially polymers of cycloolefins. Itwould be desirable to have commercial fiber glass materials that areeffective reinforcements for cycloolefinic resins that cure by thering-opening metathesis polymerization (“ROMP”) reaction. In particular,it would be desirable to have commercial fiber glass materials that areeffective reinforcements for polymers formed from dicyclopentadiene(“DCPD”) monomer.

There is a growing need for an effective fiber glass reinforcement forDCPD resins. These resins have a number of advantages over moreconventional thermoset resins, especially the widely used polyesterresins that have styrene as a co-monomer and diluent. In addition, DCPDresins may provide unique toughness and corrosion properties as comparedto conventional thermoset resins.

SUMMARY

The present invention relates to sizing compositions, to glass fibers atleast partially coated with such sizing compositions, to a variety offiber glass products at least partially coated with such sizingcompositions, and to composites formed from cycloolefins and reinforcedwith glass fibers at least partially coated with sizing compositions ofthe present invention. The present invention also relates to methods offorming fiber glass strands and methods of forming polyolefincomposites.

Fiber glass strands at least partially coated with sizing compositionsof the present invention may impart desirable or improved strength whenused to reinforce polyolefin articles, such as cycloolefins that cure byring opening metathesis polymerization. Sizing compositions of thepresent invention, in some embodiments, are believed to improve theadhesion between a fiber glass reinforcement coated with the sizingcomposition and the polyolefin resin. In addition, because a ROMPcatalyst is often used to cure cycloolefins, the sizing compositions ofthe present invention are also adapted to not poison the ROMP catalysts.

In one embodiment of the present invention, a sizing composition forglass fibers comprises a film-former comprising a polymer, wherein therepeating unit of the polymer comprises at least four carbon atoms andat least one carbon-carbon double bond, and a silane. In onenon-limiting embodiment, the at least one carbon-carbon double bond isin the backbone chain of the polymer.

In some embodiments, the film-former comprises a polymer, wherein therepeating unit of the polymer comprises four to six carbon atoms and onecarbon-carbon double bond. In other embodiments, the film-formercomprises at least one of polybutadiene, polypentadiene, andpolyhexadiene. In some embodiments, one or more repeating units in thepolymer comprises at least one pendant group. In some embodiments, theone or more pendant groups comprise at least one vinyl group. The one ormore pendant groups in some embodiments comprise at least one cyclicpendant group. In some embodiments, the one or more pendant groupsinclude others disclosed herein as well as combinations thereof.

The film-former, in some embodiments, comprises at least about 60 weightpercent of the sizing composition on a total solids basis (e.g., up toabout 90 weight percent of the sizing composition on a total solidsbasis). In some embodiments, the film-former comprises between about 70and about 85 weight percent of the sizing composition on a total solidsbasis. In other embodiments, the film-former comprises at least about 20weight percent of the sizing composition on a total solids basis.

Non-limiting embodiments of the present invention may also comprise asecond film-former. In some embodiments, the second film-former can bepresent in an amount of at least 20 weight percent on a total solidsbasis. In some such embodiments, the film-former comprising a polymer,wherein the repeating unit of the polymer comprises at least four carbonatoms and at least one carbon-carbon double bond, can be present in anamount of at least about 20 weight percent of the sizing composition ona total solids basis, and the second film-former comprises at leastabout 20 weight percent of the sizing composition on a total solidsbasis. The second film-former, in some embodiments, comprises paraffinwax and polymers or copolymers of propylene, ethylene, isobutylene,styrene, maleic anhydride, acrylate, or combinations thereof.

In one non-limiting embodiment, the film-former comprises polybutadiene.In these embodiments, the sizing composition may comprise at least about60 weight percent polybutadiene on a total solids basis (e.g., up toabout 90 weight percent polybutadiene on a total solids basis). In someembodiments, the sizing composition comprises between about 70 and about85 weight percent polybutadiene on a total solids basis. Thepolybutadiene, in some embodiments, has a number average molecular massof less than 20,000. In other embodiments, the polybutadiene has anumber average molecular mass of less than 10,000. In some embodiments,the sizing composition comprises at least about 20 weight percentpolybutadiene on a total solids basis. In some embodiments comprising atleast about 20 weight percent polybutadiene, the sizing compositions mayfurther comprise a second film-former in an amount of at least about 20weight percent on a total solids basis. The second film-former, in someembodiments, comprises paraffin wax and polymers or copolymers ofpropylene, ethylene, isobutylene, styrene, maleic anhydride, acrylate,or combinations thereof.

Silanes that can be used in various embodiments of the present inventioninclude, silanes that comprise a terminal vinyl group including, forexample, a vinylbenzyl group, a methacryloxypropyltrialkoxysilane, andcombinations thereof. In some embodiments, the silane may comprise atleast about 2 weight percent of the sizing composition on a total solidsbasis. In some embodiments, the silane may comprise at least about 5weight percent of the sizing composition on a total solids basis. Inother embodiments, the silane may comprise up to about 25 weight percentof the sizing composition on a total solids basis. The silane maycomprise between about 5 and about 25 weight percent of the sizingcomposition in some embodiments. In a further embodiment, the silane maycomprise between about 10 and about 20 weight percent of the sizingcomposition on a total solids basis.

Non-limiting embodiments of the present invention may also comprise anantioxidant and/or a surfactant. In some embodiments, the surfactantcomprises less than about 10 weight percent of the sizing composition ona total solids basis.

In some embodiments, the sizing composition is an aqueous sizingcomposition.

Another embodiment of a sizing composition for glass fibers of thepresent invention comprises a film-former comprising a polymer, whereinthe repeating unit of the polymer comprises four to six carbon atoms andone carbon-carbon double bond, in an amount between about 60 and about90 weight percent on a total solids basis; and a silane comprising aterminal vinyl group in an amount between about 5 and about 25 weightpercent on a total solids basis.

A further embodiment of a sizing composition for glass fibers of thepresent invention consists essentially of a film-former comprising apolymer, wherein the repeating unit of the polymer comprises four to sixcarbon atoms and one carbon-carbon double bond; a silane comprising aterminal vinyl group; and one or more surfactants.

The present invention also relates to fiber glass strands comprising atleast one glass fiber at least partially coated with any of the sizingcompositions of the present invention.

The present invention also relates to polyolefin composites. In oneembodiment, a polyolefin composite of the present invention comprises:(a) a plurality of glass fibers at least partially coated with any ofthe sizing compositions of the present invention; and (b) a polyolefinprepared by polymerizing a cycloolefin using a ring-opening metathesispolymerization catalyst. The polyolefin, in one non-limiting embodiment,may comprise polymers formed by polymerizing dicyclopentadiene.

These and other embodiments of the present invention are described ingreater detail in that follows.

DESCRIPTION OF DRAWINGS

FIG. 1 shows transmitted light pictures of samples during tensiletesting, for various strain levels. JBF indicates “just before failure”(one second).

FIG. 2 shows the fatigue life data and the 95/95 interval for the twomaterials. The lower bound line of these intervals indicates the lowerlimit of the region containing with 95% confidence 95% of all futuretest results.

FIG. 3 is a graph showing the evolution of the chord modulus of samplestested in fatigue up to 150 MPa.

FIG. 4 shows transmitted light pictures at certain numbers of cycles infatigue tests up to 150 MPa, illustrating the fatigue damage evolutionfor the epoxy-glass sample (FIG. 4a ) which failed at 40567 cycles, andthe pDCPD-glass sample (FIG. 4b ) which failed at 200 107 cycles.(Loading direction in these pictures is horizontal).

FIG. 5 shows a transmitted light photograph of an epoxy/ComparativeExample A sample (left) and a pDCPD F2.06/Sample 1 (right) sampleimpacted with an energy of 25 J. The scale for both pictures is thesame.

FIG. 6 is a graph showing the projected delamination size for bothmaterials and impact energies, as measured by ultrasonic c-scan.

DETAILED DESCRIPTION

For the purposes of this specification, unless otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification are to be understood as beingmodified in all instances by the term “about.” Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thefollowing specification are approximations that can vary depending uponthe desired properties sought to be obtained by the present invention.At the very least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claims, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements. Moreover, all ranges disclosed hereinare to be understood to encompass any and all subranges subsumedtherein. For example, a stated range of “1 to 10” should be consideredto include any and all subranges between (and inclusive of) the minimumvalue of 1 and the maximum value of 10; that is, all subranges beginningwith a minimum value of 1 or more, e.g. 1 to 6.1, and ending with amaximum value of 10 or less, e.g., 5.5 to 10. Additionally, anyreference referred to as being “incorporated herein” is to be understoodas being incorporated in its entirety.

It is further noted that, as used in this specification, the singularforms “a,” “an,” and “the” include plural referents unless expressly andunequivocally limited to one referent.

In some embodiments, the present invention relates to sizingcompositions for coating materials used to reinforce composites. While anumber of reinforcing materials may be used to reinforce composites,including, for example, polyester fibers, polyolefin fibers, andpolyamide fibers, embodiments of sizing compositions of the presentinvention are particularly suitable for use in coating glass fibers.

Embodiments of the present invention are directed to sizing compositionsfor glass fibers. The sizing compositions in non-limiting embodiments ofthe present invention are useful in coating glass fibers to be used asreinforcement for cycloolefins that cure by the ring-opening metathesispolymerization (“ROMP”) reaction. The polymerization of cycloolefins viaROMP reactions usually requires the presence of a ROMP catalyst to curethe composite. Examples of ROMP catalysts for polymerization ofcycloolefins include, for example, ruthenium, osmium, and molybdenummetal carbene catalysts as known to those of skill in the art.

In non-limiting embodiments, the sizing compositions of the presentinvention are useful with fiber glass reinforcements indicyclopentadiene (“DCPD”) resins. While sizing compositions areprimarily discussed herein in connection with their use on fiber glassreinforcements for reinforcing DCPD resins, it should be understood thatthe sizing compositions may also be used to at least partially coatglass fibers for reinforcing other cycloolefins that can be polymerizedby a ring opening metathesis polymerization reaction, including thosereactions set forth in U.S. Pat. No. 6,436,476 and U.S. Pat. No.6,323,296, which are hereby incorporated by reference. The sizingcompositions may also be useful with fiber glass products used toreinforce other unsaturated, free radical cure resins that do notnecessarily cure by ROMP, such as polyester.

The general reaction mechanism for polymerization of DCPD using ROMP isas follows:

One difficulty in producing compatible and effective fiber glass for useas reinforcement with polymers formed from DCPD is that the variousingredients typically used in fiber glass sizing compositions mayinhibit polymerization by “poisoning” the ROMP catalyst. As used herein,the term “poisoning”, when used in connection with a sizing compositionor components of a sizing composition, refers to a sizing composition ora component thereof that negatively affects the polymerization of acycloolefin by, for example, inhibiting, slowing, preventing, orterminating the desired polymerization process. For example, a componentof a sizing composition may react with the ROMP catalyst to produce aspecies that is not a catalyst, and thereby prevent the ROMP catalystfrom polymerizing the monomer. Consequently, there have been continuingefforts by catalyst suppliers to reduce the sensitivity of the ROMPcatalyst chemistry to sizing components. It would be desirable to have asizing composition that would not limit curing of the DCPD, while stillproducing composites with an acceptable shear strength.

The present invention advantageously provides sizing compositions thatare compatible with ROMP catalysts, such that the sizing compositions donot substantially inhibit polymerization by poisoning the ROMP catalyst.The sizing compositions of the present invention, when at leastpartially coated on glass fibers used to reinforce polymerizedcycloolefins, also provide composites having adequate or desirable shearstrengths in some embodiments. The selection of components and theirrelative amounts can provide such features and others.

In one non-limiting embodiment, a sizing composition of the presentinvention comprises at least one film-former comprising a polymer,wherein the repeating unit of the polymer comprises at least four carbonatoms and at least one carbon-carbon double bond, and at least onesilane.

Film-formers useful in non-limiting embodiments of the present inventionhave relatively low potentials for poisoning the ROMP catalyst used topolymerize cycloolefinic resins. In some embodiments, film-formersuseful in non-limiting embodiments of the present invention may be freefrom (i.e., may not include) primary amines, thiols, terminal epoxides,functional groups having active oxygen groups (e.g., hydroperoxides andactivated epoxides), acetylenes, and vinyl ethers. To avoid poisoningROMP catalysts, film-formers useful in non-limiting embodiments of thepresent invention may be substantially free from, or may only include ina limited way (i.e., less than 1 weight percent, less than 0.5 weightpercent, less than 0.1 weight percent, less than 0.05 weight percent, orless than 0.01 weight percent by weight), the following functionalgroups: primary amines, thiols, terminal epoxides, functional groupshaving active oxygen groups (e.g., hydroperoxides and activatedepoxides), acetylenes, and vinyl ethers. Such structures are believed topoison and/or adversely affect the operation of the ROMP catalyst. Asnoted below, silanes used in embodiments of the present invention mayalso not include these functional groups. Certain constituents that canact as Lewis bases may also not be desirable for use as a film-former inembodiments of the present invention. Film-formers useful in embodimentsof the present invention can also assist in holding fiber glassfilaments together to form a strand that can be wet out by liquidresins.

The film-formers, in some embodiments, comprise a polymer that includesat least one carbon-carbon double bond in the backbone chain of thepolymer. In some embodiments, the repeating unit (i.e., the monomericunit) of the polymer comprises four to six carbon atoms and onecarbon-carbon double bond. The film-formers, in some embodiments, cancomprise at least one of polybutadiene, polypentadiene, andpolyhexadiene. Other common film-formers that would not poison the ROMPcatalyst (e.g., by reacting with the ROMP catalyst to form anon-catalytic species) can also be used as additional film-formers insome embodiments.

In some embodiments, the backbone chain of the polymer can include thefollowing polybutadiene repeating unit comprising four carbon atoms andone carbon-carbon double bond, according to one of the structures shownbelow:(—CR¹R²—CR³═CR⁴—CR⁵R⁶—)_(n);(—CR¹═CR²—CR³R⁴—CR⁵R⁶—)_(n); or(—CR¹R²—CR³R⁴—CR⁵═CR⁶—)_(n).

In the polybutadiene repeating unit, “n” is an integer greater than 1.In some embodiments, “n” is an integer from 20 to 400. Also in thepolybutadiene repeating unit, R¹, R², R³, R⁴, R⁵, and R⁶ are eachindependently hydrogen, an aliphatic moiety, a heteroaliphatic moiety, acarbocyclic moiety, or a heterocyclic moiety. In some embodiments, eachof R¹-R⁶ is hydrogen. In some embodiments, one or more of R¹, R², R³,R⁴, R⁵, and R⁶ can be a pendant group or a linking molecule thatconnects the backbone to a pendant group. Optionally, the polybutadienerepeating unit has a trans configuration.

Optionally, one or more groups can be pendant from the backbone chain ofthe polymer. In some embodiments, one or more pendant groups can beattached to one or more of the repeating units. For example, for apolymer with 100 repeating units (i.e., n is 100), pendant groups couldbe attached to from 0 to 100 of the units. In other words, thepercentage of pendant group-containing repeating units in the polymercan be 100% or less (e.g., 90% or less, 80% or less, 70% or less, 60% orless, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less,5% or less, or 1% or less), based on the total number of repeating unitsin the polymer. In some embodiments, one or more of R¹, R², R³, R⁴, R⁵,and R⁶ can include a pendant group. In other embodiments, two R groupson adjacent carbons (e.g., R¹ and R³, R³ and R⁴, or R⁴ and R⁵) cancombine together, forming a carbocyclic moiety or a heterocyclic moiety.In some non-limiting embodiments, the pendant group can include a vinylgroup. In other non-limiting embodiments, the pendant group can includea cyclic group, such as a cyclopentene group. In some non-limitingembodiments, the pendant group can include maleic anhydride. Differentpendant groups can be present in the polymer in varying amounts. Forexample, for a polymer with 100 repeating units (i.e., n is 100), avinyl pendant group can be attached to from 15-25% of the repeatingunits in the polymer and the remainder of the repeating units in thepolymer can be unmodified (i.e., no pendant groups attached). In anotherembodiment, for a polymer with 100 repeating units (i.e., n is 100), avinyl pendant group can be attached to from 40-55% of the repeatingunits in the polymer, a cyclic pendant group can be attached to from15-20% of the repeating units in the polymer, and the remainder of therepeating units in the polymer can be unmodified (i.e., no pendantgroups attached). In one non-limiting embodiment, the at least onefilm-former may be a functionalized polymer, such as a maleic anhydridefunctionalized polymer. For example, the at least one film-former may bea maleic anhydride functionalized polybutadiene. The maleic anhydridefunctionalized polymers can be prepared by reacting maleic anhydridewith a carbon-carbon double bond of the backbone chain of the polymerunder thermal conditions to form a maleic anhydride adduct.

In one non-limiting embodiment, the at least one film-former comprises apolybutadiene having a number average molecular mass of less than20,000. For example, the polybutadiene can have a number averagemolecular mass of 17,500 or less; 15,000 or less; 12,500 or less; 10,000or less; 7,500 or less; 5,000 or less; or 3,000 or less in variousembodiments.

Examples of suitable polybutadienes useful as film-formers in anon-limiting embodiment of the present invention include functionalizedand non-functionalized polybutadienes, such as those polybutadienescommercially available from Synthomer, Inc. (Harlow, United Kingdom),under the Lithene product name. For example, suitable non-functionalpolybutadienes include, without limitation, Lithene Ultra AL, apolybutadiene having a number average molecular mass of 1,000 andcontaining vinyl and cyclic pendant groups; Lithene Ultra AH, apolybutadiene having a number average molecular mass of 1,800 andcontaining vinyl and cyclic pendant groups; Lithene Ultra PH, apolybutadiene having a number average molecular mass of 2,600 andcontaining vinyl pendant groups; Lithene Ultra PM4, a polybutadienehaving a number average molecular mass of 1,500 and containing vinylpendant groups; Lithene Ultra P4-25P, a polybutadiene having a numberaverage molecular mass of 2,600 and containing vinyl pendant groups;Lithene Ultra P4-150P, a polybutadiene having a number average molecularmass of 3,200 and containing vinyl pendant groups; Lithene UltraN4-5000, a polybutadiene having a number average molecular mass of 5,000and containing vinyl pendant groups; and Lithene Ultra N4-9000, apolybutadiene having a number average molecular mass of 9,000 andcontaining vinyl pendant groups.

Suitable functionalized polybutadienes include maleic acidfunctionalized polybutadienes, such as Lithene Ultra AL-15MA, a maleicacid functionalized polybutadiene having a number average molecular massof 1,300; Lithene Ultra PM4-7.5MA, a maleic acid functionalizedpolybutadiene having a number average molecular mass of 1,600; LitheneUltra N4-5000-15MA, a maleic acid functionalized polybutadiene having anumber average molecular mass of 5,750; Lithene Ultra N4-B-10MA, amaleic acid functionalized polybutadiene having a number averagemolecular mass of 8,200; and Lithene Ultra N4-9000-10MA, a maleic acidfunctionalized polybutadiene having a number average molecular mass of9,500.

In another non-limiting embodiment, the at least one film-former maycomprise a copolymer. For example, the at least one film-former maycomprise a copolymer formed from a first monomer unit and one or moreadditional monomer units. The first monomer unit may comprise at leastfour carbon atoms (e.g., from four to six carbon atoms). The one or moreadditional monomer units may be any copolymerizable monomer, as known tothose of skill in the art. For example, the one or more additionalmonomer units may include vinylaromatic monomer units (e.g., styrene),acrylate monomer units, methacrylate monomer units, acrylonitrilemonomer units, and/or olefin monomer units.

Optionally, the at least one film-former may comprise astyrene-butadiene copolymer. An example of a styrene-butadiene copolymeruseful as a film-former in a non-limiting embodiment of the presentinvention comprises Plextol X-9110, commercially available fromPolymerLatex GmbH. of Marl, Germany.

Optionally, the at least one film-former may comprise a styrene-acrylatecopolymer. An example of a styrene-acrylate copolymer useful as afilm-former in a non-limiting embodiment of the present inventioncomprises Plextol X-4020 and Plextol X-4545, both commercially availablefrom PolymerLatex GmbH. of Marl, Germany.

The sizing composition can include one film former in some embodiments,or multiple film-formers in others. The one or more film-formers aregenerally present in the sizing composition in an amount of at least 60weight percent, the percentages based on the total solids of the sizingcomposition. Optionally, the one or more film-formers are present in thesizing composition in an amount of at least 65 weight percent, at least70 weight percent, at least 75 weight percent, at least 80 weightpercent, or at least 85 weight percent in other embodiments. The one ormore film-formers are present in the sizing composition in an amount ofup to about 90 weight percent, the percentages based on the total solidsof the sizing composition in some embodiments. In some embodiments, theone or more film-formers are present in the sizing composition in anamount of between about 70 and about 85 weight percent.

In some non-limiting embodiments, the sizing composition includes afirst film-former and a second film-former, wherein the firstfilm-former comprises a polymer, wherein the repeating unit of thepolymer comprises at least four carbon atoms and at least onecarbon-carbon double bond (including, for example, any such polymersdescribed above). In one non-limiting embodiment, the first film-formercomprises at least about 20 weight percent of the sizing composition ona total solids basis. Optionally, the first film-former can comprise atleast about 25 weight percent, at least 30 weight percent, at least 35weight percent, at least 40 weight percent, or at least 45 weightpercent of the sizing composition on a total solids basis in variousembodiments.

Suitable second (and other additional) film-formers include, forexample, a non-reactive polymer. In some embodiments, the secondfilm-former can include paraffin wax and polymers or copolymers ofpropylene, ethylene, isobutylene (e.g., polyisobutylene), styrene (e.g.,polystyrene), maleic anhydride, acrylate (e.g., polymethylmethacrylate),or combinations thereof. Examples of suitable second film-formers in anon-limiting embodiment of the present invention comprise MichemLub 723,a paraffin wax dispersion commercially available from Michelman, Inc. ofCincinnati, Ohio; Aquacer 1605, a polypropylene dispersion commerciallyavailable from Byk of Wesel, Germany; Novacer 1200, a polyethylenedispersion commercially available from Byk; and ML 93135, a polyethylenedispersion commercially available from Michelman, Inc. The second (oradditional) film-formers can be present in the sizing composition in anamount of less than about 50 weight percent (e.g., less than about 45weight percent, less than about 40 weight percent, less than about 30weight percent, less than about 25 weight percent, or less than about 20weight percent) on a total solids basis. In some embodiments, a firstfilm-former comprising polybutadiene is present in an amount of at leastabout 20 weight percent of the sizing composition on a total solidsbasis and a second film-former comprising paraffin wax is present in anamount of at least about 10 weight percent of the sizing composition ona total solids basis. In other embodiments, a first film-formercomprising polybutadiene is present in an amount of at least about 50weight percent of the sizing composition on a total solids basis and asecond film-former comprising paraffin wax is present in an amount of atless than about 45 weight percent of the sizing composition on a totalsolids basis. In some embodiments, a first film-former comprisingpolybutadiene is present in an amount of at least about 50 weightpercent of the sizing composition on a total solids basis and a secondfilm-former comprising paraffin wax is present in an amount of at lessthan about 30 weight percent of the sizing composition on a total solidsbasis. A first film-former comprising polybutadiene is present in anamount of at least about 50 weight percent of the sizing composition ona total solids basis and a second film-former comprising paraffin wax ispresent in an amount of at less than about 20 weight percent of thesizing composition on a total solids basis in some embodiments.

Sizing compositions of the present invention further comprise one ormore silanes. The one or more silanes are capable of reacting orotherwise interacting with cyclic olefinic resins, such asdicyclopentadiene (“DCPD”), during cure. Silanes that are capable ofreacting with DCPD, in some non-limiting embodiments, can participate inthe polymerization and cross-linking mechanism of the DCPD resin. Thesilanes can have a relatively low potential to poison the ROMP catalyst.The one or more silanes are also capable of reacting or otherwiseinteracting with the film-former, such as the polybutadiene film-formerdescribed herein.

In some non-limiting embodiments, silanes useful in the sizings of thepresent invention comprise a terminal vinyl group. As understood tothose of skill in the art, a “terminal” vinyl group means that thedouble bond occurs at the end of the hydrocarbon radical opposite fromthe end bonded to the silicone atom in the silane.

In some embodiments, suitable silanes comprising a terminal vinyl groupcan include silanes comprising a vinylbenzyl group. An example of acommercially available silane comprising a vinylbenzyl group isDYNASYLAN® 1172N-2-(vinylbenzylamino)-ethyl-3-aminopropyltrimethoxysilane from DegussaAG of Dusseldorf, Germany, which has the following structure:

Another example of a commercially available silane comprising avinylbenzyl group is DYNASYLAN® 1175 from Degussa AG of Dusseldorf,Germany, which is believed to have the same structure as DYNASYLAN®1172. Another example of a commercially available silane comprising avinylbenzyl group is Z-6032N-2-(vinylbenzylamino)-ethyl-3-aminopropyltrimethoxysilane from DowCorning. DYNASYLAN 1172 is provided in acetic acid while DYNASYLAN 1175and Z-6032 are provided in hydrochloric acid. Another example of acommercially available silane comprising a vinylbenzyl group is KBM-974,which is a[3-[[2-[(vinylbenzyl)amino]ethyl]amino]propyl]trimethoxysilanecommercially available from Shin-Etsu Chemical Co., Ltd. of Tokyo,Japan.

In some non-limiting embodiments, silanes useful in the sizings of thepresent invention comprise shorter chain silanes having terminal vinylgroups that may provide less adhesion between the fiber glassreinforcement and the polyolefin. Examples of suitable silanes include,for example, vinyltrialkoxysilanes. In some embodiments, a suitablevinyltrialkoxysilane includes Silquest A-151, a vinyltriethoxysilanecommercially available from Momentive Performance Materials, Inc.(Columbus, Ohio). A further example of a suitable silane, in someembodiments, includes methacryloxypropyltrialkoxy silanes such as3-methacryloxypropyltrialkoxysilane, commercially available as SilquestA-174 from Momentive Performance Materials, Inc. (Columbus, Ohio).

In another non-limiting embodiment, a silane useful in a sizing of thepresent invention comprises a norbornenyl-functional silane.Norbornenyl-functional silanes useful in the present invention mayinclude, for example, norbornenyl trimethoxysilanes and norbornenyltriethoxysilanes having four or more carbon atoms in a chain between thesilicon atom and the norbornenyl group.

Other potentially useful silanes may include carbons in the chain havingfunctional groups attached, although any such functionality wouldpreferably not poison the ROMP catalyst. Examples of undesirablefunctional groups are set forth above in connection with thefilm-former. Such undesirable functional groups may, for exampleinclude: primary amines, thiols, terminal epoxides, hydroperoxides,activated epoxides, acetylenes, and vinyl ethers.

The at least one silane can generally be present in the sizingcomposition in an amount from at least about 5 weight percent up toabout 25 weight percent, the percentages based on the total solids ofthe sizing composition. The at least one silane, in a furthernon-limiting embodiment, may be present in an amount from 5 weightpercent to 15 weight percent or from 10 weight percent to 20 weightpercent, the percentages based on the total solids of the sizingcomposition.

Embodiments of sizing compositions of the present invention may comprisemultiple silanes as described herein. In these embodiments, at least oneof the silanes is capable of reacting with cyclic olefinic resins, suchas dicyclopentadiene (“DCPD”), during cure. When multiple silanes areused, each silane can have a low potential to poison the ROMP catalyst(e.g., react with the ROMP catalyst to produce a species that is not acatalyst). The potential to avoid poisoning the ROMP catalyst can beavoided by not using silanes that include, for example, the followingfunctional groups: primary amines, thiols, terminal epoxides,hydroperoxides, activated epoxides, acetylenes, and vinyl ethers.

Depending on the particular film-former used, one or more emulsifyingagents or surfactants may be used to assist in dispersing thefilm-former in water or an aqueous solution. Emulsifying agents can alsoassist in emulsifying or dispersing other components of the sizingcompositions in some embodiments. For example, when the film-formercomprises a polymer, wherein the repeating unit of the polymer comprisesat least four carbon atoms and at least one carbon-carbon double bond(including, for example, any such polymers described above), it may bebeneficial to utilize one more emulsifying agents or surfactants toassist in dispersing the polymer in an aqueous sizing composition.

Non-limiting examples of suitable emulsifying agents can includepolyoxyalkylene block copolymers, ethoxylated alkyl phenols,polyoxyethylene octylphenyl glycol ethers, ethylene oxide derivatives ofsorbitol esters, polyoxyethylated vegetable oils, ethoxylatedalkylphenols, and nonylphenol surfactants. Examples of commerciallyavailable emulsifying agents useful in embodiments of the presentinvention can include Pluronic F-108, which is a polyoxyalkylene blockcopolymer and which is commercially available from BASF Corp. (FlorhamPark, N.J.); Alkamuls EL-719, which is an ethoxylated castor oil andwhich is commercially available from Rhodia (Courbevoie, France);Genapol UD 050 from Clariant Corporation of Mt. Holly, N.C.; andLutensol OP-10, which is an octylphenol ethoxylate and which iscommercially available from BASF Corp.

As indicated above, embodiments of the present invention can utilize oneor more emulsifying agents or surfactants. Multiple emulsifying agentscan be used in some embodiments to assist in providing a more stableemulsion. Multiple emulsifying agents can be used in amounts effectiveto disperse hydrophobic components, such as certain film-formers, inwater or an aqueous solution. For example, when the film-formercomprises a polymer, wherein the repeating unit of the polymer comprisesat least four carbon atoms and at least one carbon-carbon double bond(including, for example, any such polymers described above), it may bebeneficial to utilize multiple emulsifying agents or surfactants toassist in dispersing the polymer in an aqueous sizing composition. Insome non-limiting embodiments of sizing compositions that include one ormore emulsifying agents or surfactants, the total amount of emulsifyingagents or surfactants can comprise up to 20 weight percent of the sizingcomposition based on total solids. In other non-limiting embodiments,the total amount of emulsifying agents can comprise up to 17 weightpercent of the sizing composition based on total solids. In othernon-limiting embodiments, the total amount of emulsifying agents cancomprise up to 16 weight percent of the sizing composition based ontotal solids. In some embodiments, the total amount of emulsifyingagents can comprise 10 or more weight percent of the sizing compositionbased on total solids. The total amount of emulsifying agents, in someembodiments, can comprise between 10 and 20 weight percent of the sizingcomposition based on total solids.

In some non-limiting embodiments, sizing compositions of the presentinvention may further include one or more antioxidants. One or moreantioxidants can be used in some embodiments to prevent oxidative dryingof film-formers in dried products. The one or more antioxidants can alsobe useful in suppressing skin formation and discoloration of certainfilm-formers, such as polybutadiene and similar film-formers.Non-limiting examples of suitable antioxidants can include stericallyhindered phenols, hindered amine light stabilizers (HALS), andphosphites. Examples of commercially available antioxidants useful inembodiments of the present invention can include butylatedhydroxytoluene (BHT); sodium hypophosphite;N,N′-diphenyl-p-phenylenediamine (DPPD), commercially available fromWestco (Western Reserve Chemical Corporation, Stow, Ohio);ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate],commercially available as Irganox 245 from BASF;4,6-bis(octylthiomethyl)-o-cresol, commercially available as Irganox1520 from BASF; 4,6-bis(dodecylthiomethyl)-o-cresol, commerciallyavailable as Irganox 1726 from BASF;Octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate, commerciallyavailable as Irganox 1076 from BASF; Irgastab PVC 76, a heat stabilizercommercially available from BASF; tris(2,4-ditert-butylphenyl)phosphite,commercially available as Irgafos 168 from BASF; Tinuvin 765, a liquidhindered amine light stabilizer commercially available from BASF;Aquanox TD, a water-based antioxidant commercially available fromAquaspersions Ltd. (Halifax, United Kingdom); and Chimasorb 119, ahindered amine light stabilizer commercially available from Sabo S.p.A.(Levate, Italy). Non-limiting examples of phosphites that can be used insome embodiments of the present invention also include those disclosedin U.S. Pat. No. 6,207,737, which is hereby incorporated by reference.

The one or more antioxidants can generally be present in the sizingcomposition in an amount of up to about 10 weight percent based on thetotal solids of the sizing composition. The one or more antioxidants, ina further non-limiting embodiment, may be present in an amount from 0.1weight percent to 10 weight percent or from 1 weight percent to 5 weightpercent, the percentages based on the total solids of the sizingcomposition.

In addition to at least one film-former and at least one silane, sizingcompositions of the present invention may further comprise one or morelubricants. In one non-limiting embodiment, the lubricant comprises atleast one non-ionic lubricant. As used herein, the term “non-ionic” isused in a manner normally appreciated by those of ordinary skill in theart. Non-ionic lubricants useful in embodiments of the present inventionpreferably do not include reactive groups or other structures that mightpoison the ROMP catalyst or negatively affect the polymerization of thecycloolefins as described herein.

Examples of non-ionic lubricants useful in embodiments of the presentinvention comprise ethoxylated fatty alcohols, such as ethoxylatedmonooleate, ethoxylated di-oleate, ethoxylated monotallate andethoxylated di-tallate. An example of a suitable ethoxylated di-tallateis available from BASF Corporation under the product name MAPEG 600 DOT.MAPEG 600 DOT is a polyethylene glycol ditallate having an averagemolecular weight of 600. An example of a suitable ethoxylated di-oleateis available from BASF Corporation under the product name MAPEG 600 DO.MAPEG 600 DO is a polyethylene glycol di-oleate having an averagemolecular weight of 600. Other examples of ethoxylated di-tallates andethoxylated di-oleates, as well as ethoxylated monooleates andethoxylated monotalates, are also available from BASF Corporation underthe MAPEG product line. A further example of a non-ionic lubricantuseful in embodiments is polyethylene glycol monolaurate, which iscommercially available from The HallStar Company as HALLSTAR PEG 600 ML.

The at least one non-ionic lubricant can generally be present in thesizing composition in an amount from 10 weight percent to 55 weightpercent, the percentages based on the total solids of the sizingcomposition. The at least one non-ionic lubricant, in a furthernon-limiting embodiment, may be present in an amount from 25 weightpercent to 35 weight percent, the percentages based on the total solidsof the sizing composition.

The sizing composition of the present invention may further comprise atleast one cationic lubricant. In another non-limiting embodiment, thesizing composition may comprise at least one cationic lubricant withouta non-ionic lubricant. As used herein, the term “cationic” is used in amanner normally appreciated by those of ordinary skill in the art.Cationic lubricants advantageously protect against fiber-to-fiberabrasion. In one non-limiting embodiment, the concentration of thecationic lubricant is sufficiently low to avoid poisoning the ROMPcatalyst. While the cationic lubricant may include functional groupsthat may poison the ROMP catalyst (e.g., secondary amines), somecationic lubricant may be needed to protect against fiber-to-fiberabrasion. Accordingly, embodiments may use cationic lubricants inamounts that protect against fiber-to-fiber abrasion withoutsignificantly affecting the function of the ROMP catalyst.

The loss on ignition of the cationic lubricant in one non-limitingembodiment is 0.01% or less. While generally most cationic lubricantsused in fiber glass sizing compositions will be suitable for use in thepresent invention, examples of cationic lubricants useful innon-limiting embodiments of the present invention include carboxylicacid salts of amidoamines. Examples of suitable carboxylic acid salts ofamidoamines include Emery 6717L, available from Cognis Corporation, CatX available from Rhone Poulenc, and Alubraspin 261 available from BASFCorp. Further examples of suitable cationic lubricants include LubrilCat-X/VC, commercially available from Rhodia of Cranbury, N.J., andKatax 6717, commercially available from Pulcra Chemical of Geretsried,Germany.

The at least one cationic lubricant may be present in the sizingcomposition in an amount from 0 weight percent to 5 weight percent, thepercentages based on the total solids of the sizing composition. Smalleramounts of amine-containing cationic lubricants may be used in suchembodiments due to the potential to poison the ROMP catalyst in someembodiments. In some non-limiting embodiments, the at least one cationiclubricants may be generally present in the sizing composition in anamount from 0 weight percent to 2 weight percent, the percentages basedon the total solids of the sizing composition. The at least one cationiclubricant, in other non-limiting embodiments, may be generally presentin the sizing composition in an amount from 0 weight percent to 1 weightpercent, the percentages based on the total solids of the sizingcomposition.

The sizing composition of the present invention may further comprise atleast one anionic lubricant. In another non-limiting embodiment, thesizing composition may comprise at least one anionic lubricant without acationic lubricant or a non-ionic lubricant. As used herein, the term“anionic” is used in a manner normally appreciated by those of ordinaryskill in the art. Example of a suitable anionic lubricant for use in thepresent invention include partial esters of a branched carboxylic acidcopolymer, such as Ketjenlube 522 partial ester (also sold as DapralGE202). Ketjenlube 522 partial ester is commercially available from AkzoChemie America of Chicago, Ill.

The sizing composition can also optionally contain other ingredientswhich are known to those skilled in the art to be useful in fiber glasssizing compositions, such as antifoaming agents, biocides, humectantsand the like. The sizing composition can be prepared by any method knownto those skilled in the art, and applied to the fibers and/or fillers byany method known in the art.

The present invention also relates to fiber glass products comprising aplurality of glass fibers at least partially coated with a sizingcomposition of the present invention. In one non-limiting embodiment,the fiber glass product is a fiber glass strand. The fiber glass strandmay be wound into a cylindrical package and dried using techniques knownto those of ordinary skill in the art. These individual packages may beshipped to a composite manufacturer to make a reinforced composite.Composite manufacturers typically use strands from a plurality ofpackages to make a composite. In another non-limiting embodiment, aglass fiber strand may be directly wound into a fiber glass roving,dried, and shipped to a composite manufacturer. In non-limitingembodiments, a roving may comprise 4000 or more fibers, the fibershaving diameters between 13 and 35 microns. In other non-limitingembodiments, the rovings are assembled rovings comprising as many as10,000 or more fibers, the fibers having diameters between 10 and 23microns. In some applications, chopped fiber glass strands and fiberglass mats can be used.

In non-limiting embodiments of the present invention, the loss onignition of the sizing on the fiber glass can generally be between 0.1and 2.0%. In other non-limiting embodiments, the loss on ignition cangenerally be between 0.1 and 1.5%. The loss on ignition of the sizing onthe fiber glass, in other non-limiting embodiments, can generally bebetween 0.1% and 0.8%.

The present invention also relates to methods of forming a plurality ofglass fibers having sizings of the present invention applied thereon.Any glass fiber suitable for reinforcing can suitably be treated inaccordance with the present invention. Non-limiting examples of glassfibers suitable for use in the present invention can include thoseprepared from fiberizable glass compositions such as “E-glass”,“A-glass”, “C-glass”, “S-glass”, “ECR-glass” (corrosion resistantglass), and fluorine and/or boron-free derivatives thereof.

The glass fibers of the present invention can be formed in any suitablemethod known in the art, for forming glass fibers. For example, glassfibers can be formed in a direct-melt fiber forming operation or in anindirect, or marble-melt, fiber forming operation. In a direct-meltfiber forming operation, raw materials are combined, melted andhomogenized in a glass melting furnace. The molten glass moves from thefurnace to a forehearth and into fiber forming apparatuses where themolten glass is attenuated into continuous glass fibers. In amarble-melt glass forming operation, pieces or marbles of glass havingthe final desired glass composition are preformed and fed into a bushingwhere they are melted and attenuated into continuous glass fibers. If apremelter is used, the marbles are fed first into the premelter, melted,and then the melted glass is fed into a fiber forming apparatus wherethe glass is attenuated to form continuous fibers. In the presentinvention, the glass fibers can be formed by the direct-melt fiberforming operation. For additional information relating to glasscompositions and methods of forming the glass fibers, see K.Loewenstein, The Manufacturing Technology of Continuous Glass Fibres,(3d Ed. 1993), at pages 30-44, 47-103, and 115-165, which arespecifically incorporated by reference herein. Immediately afterformation, the filaments are at least partially coated with anembodiment of the sizing composition described above. The application ofsizing to glass fibers is well known in the art and can be accomplishedby conventional methods such as a belt applicator, a “kiss-roll”applicator or by spraying. The glass fibers are then gathered into atleast one strand, and collected into a forming package on a winder. Seegenerally K. Loewenstein, The Manufacturing Technology of ContinuousGlass Fibres, (3d Ed. 1993).

The present invention also relates to polyolefin composites reinforcedwith sized glass fibers, wherein the sizing comprises a sizingcomposition of the present invention. In one non-limiting embodiment,the polyolefin comprises polymers formed from cyclic olefins. In afurther non-limiting embodiment, the cyclic olefins are cured by ROMPcatalysts. In another non-limiting embodiment, the polyolefin comprisespolymers formed from DCPD. In a further non-limiting embodiment, theDCPD monomer is cured by ROMP catalysts. In another non-limitingembodiment, the sizing compositions of the present invention can be usedto at least partially coat glass fibers for use in reinforcingcomposites formed through other unsaturated polymerization reactions,such as reactions involving unsaturated polyesters, acrylics, and thelike, as known to those of skill in the art.

In embodiments where the composite comprises polymers formed from cyclicolefins, such as pDCPD, glass fibers comprising embodiments of sizingcompositions of the present invention can be added to a curablecomposition. The curable composition can comprise, in some suchembodiments, a cyclic olefin (e.g., DCPD), a metathesis catalyst forpolymerizing the cyclic olefin, a modifier compound, and a curing agentfor the modifier compound. The modifier compound can be present in thecurable composition in amount between about 0.1 and 30 weight percentbased on the total weight of the composition in some embodiments. Themodifier compound, in some embodiments, can be present in the curablecomposition in amount between about 3 and 20 weight percent based on thetotal weight of the composition. The curing agent can be present in anamount between about 0.1 and about 10 weight percent based on the totalweight of the curing composition in some embodiments. The curing agent,in some embodiments, can be present in an amount between about 0.2 andabout 1 weight percent based on the total weight of the curingcomposition. The curing agent can comprise a radical initiator such as anon-cyclic peroxide in some embodiments. In some embodiments, thecurable composition comprises a cyclic olefin (e.g., DCPD), a metathesiscatalyst for polymerizing the cyclic olefin, 0.1-30 wt. % of a modifiercompound based on the total weight of the composition, and 0.1-10 wt. %of a curing agent for the modifier compound based on the total weight ofthe composition. Composites formed from such curable compositions andglass fibers at least partially coated with sizing compositions of thepresent invention can be formed using techniques known to those of skillin the art.

In other non-limiting embodiments, composites of the present inventionhave a bonding strength of greater than 4,000 pounds per square inch(psi) as determined by short-beam shear (SBS) testing. In othernon-limiting embodiments, the composites have a bonding strength ofgreater than 5,000 psi as determined by SBS testing. Composites of thepresent invention, in other non-limiting embodiments, have a bondingstrength of greater than 6,000 psi as determined by SBS testing.

It was observed that composites utilizing rovings coated with sizings ofthe present invention can exhibit improved glass-matrix resin bondingstrengths over composites utilizing conventional fiber glassreinforcements. Short-beam shear testing in accordance with ASTM 2344 isone way in which glass-matrix resin bonding strength can be measured.

Embodiments of the present invention will now be illustrated in thefollowing specific, non-limiting examples.

EXAMPLES

Sizing compositions were prepared in accordance with the formulationsset forth in Table 1. These formulations represent non-limitingembodiments of sizing compositions of the present invention. Example 1is one embodiment of a sizing composition that can be used, for example,on glass fibers in applications where a strong level of adhesion isdesired. Example 2 is another embodiment of a sizing composition thatcan be used, for example, on glass fibers in applications where a lessstrong level of adhesion to a substrate, such as in ballisticsoperations, is desired.

TABLE 1 Component 1 2 Silane A with  3709 g vinylbenzyl¹ (15.5%) SilaneB with  2360 g terminal (15.5%) vinyl² Polybutadiene  6584 g  6584 gPolymer³ (77.3%) (77.3%) Emulsifying  307 g  307 g Agent⁴  (3.6%) (3.6%) Nonionic  307 g  307 g Surfactant⁵  (3.6%)  (3.6%) Water for13169 g 13169 g Polybutadiene Polymer Emulsion Total Mix 56775 g 56775 gAmount Total Percent   15%   15% Solids ¹DYNASYLAN 1175 from Degussa AG.²SILQUEST A-151 from Momentive Performance Materials, Inc. ³LITHENEP4-25P from Synthomer, Inc. ⁴PLURONIC F-108 polyoxyalkylene blockcopolymer from BASF Corp. ⁵GENAPOL UD 050 from Clariant Corporation.

Additional formulations representing non-limiting embodiments of sizingcompositions of the present invention are provided in Tables 2 and 3 asExamples 3-15.

TABLE 2 Component 3 4 5 6 7 8 9 Silane A with 98.6 g 493.0 g 98.6 g 98.6g 98.6 g vinylbenzyl⁶ (15.5%) (47.8%) (11.8%) (15.5%) (16.7%) Silane Bwith 62.7 g 313.6 g terminal (15.5%) (47.8%) vinyl⁷ Polybutadiene 175 gPolymer A⁸ (77.3%) Polybutadiene 175 g 175 g 175 g 175 g Polymer B⁹(77.3%) (47.8%) (77.3%) (47.8%) Polybutadiene 175 g Polymer C¹⁰ (59.2%)Styrene- 350 g butadiene (83.3%) Copolymer¹¹ Emulsifying 8.2 g 8.2 g 8.2g 8.2 g 8.2 g Agent¹² (3.6%) (2.2%) (3.6%) (2.2%) (3.6%) Nonionic 8.2 g8.2 g 8.2 g 8.2 g 8.2 g Surfactant¹³ (3.6%) (2.2%) (3.6%) (2.2%) (3.6%)Water for 350 g 350 g 350 g 350 g 350 g Polybutadiene (0%) (0%) (0%)(0%) (0%) Polymer emulsion Hot Water for 4375 g Polybutadiene (0%)Polymer solution¹⁴ Ammonia 343 g (25%) (29.0%) Total Mix 7000 g 7000 g7000 g 7000 g 7000 g 7000 g 7000 g Amount Total Percent 3.23% 5.23%3.23% 5.23% 4.23% 3.23% 3.00% Solids ⁶DYNASYLAN 1175 from Degussa AG.⁷SILQUEST A-151 from Momentive Performance Materials, Inc. ⁸LITHENEP4-25P from Synthomer, Inc. ⁹LITHENE P4-150P from Synthomer Inc.¹⁰LITHENE AL-15MA from Synthomer Inc. ¹¹PLEXTOL X9110 from PolymerLatexGmbH. ¹²SYNPERONIC PE/F108 ethoxylated polypropylene oxide from CrodaInternational. ¹³Blend MPG (monopropylene glycol) from Chemische WerkeKluthe GMBH.

TABLE 3 Component 10 11 12 13 14 15 Silane A with 84.5 g 42.2 gvinylbenzyl¹⁵ (15.5%) (7.7%) Silane B with 53.7 g terminal vinyl¹⁶(15.5%) Silane C (3- 36.1 g methacryloxypropyl- (15.5%)trimethoxysilane)¹⁷ Silane D (octenyl)¹⁸ 75 g 37.5 g (15.5%) (7.7%)Silane E 36.3 g (norbornenyl silane) (15.5%) Polybutadiene 150 g 150 g150 g 150 g 150 g 150 g Polymer¹⁹ (77.3%) (77.3%) (77.3%) (77.3%)(77.3%) (77.3%) Emulsifying Agent²⁰ 7.0 g 7.0 g 7.0 g 7.0 g 7.0 g 7.0 g(3.6%) (3.6%) (3.6%) (3.6%) (3.6%) (3.6%) Nonionic 7.0 g 7.0 g 7.0 g 7.0g 7.0 g 7.0 g Surfactant²¹ (3.6%) (3.6%) (3.6%) (3.6%) (3.6%) (3.6%)Water for  300 g  300 g  300 g  300 g  300 g  300 g PolybutadienePolymer Emulsion Total Mix Amount 6000 g 6000 g 6000 g 6000 g 6000 g6000 g Total Percent Solids 3.23 3.23 3.23 3.23 3.23 3.23 ¹⁴Hot water isat 82° C. ¹⁵DYNASYLAN 1175 from Degussa AG. ¹⁶SILQUEST A-151 fromMomentive Performance Materials, Inc. ¹⁷DYNASYLAN MEMO from Degussa AG.¹⁸SILBLOCK WMS from Momentive Performance Materials, Inc. ¹⁹LITHENEP4-25P from Synthomer, Inc. ²⁰SYNPERONIC PE/F108 ethoxylatedpolypropylene oxide from Croda International. ²¹Blend MPG (monopropyleneglycol) from Chemische Werke Kluthe GMBH.Preparation of Sizing Compositions

To prepare the sizing compositions shown as Examples 1-6, 8, and 10-15in Tables 1-3, the specified amount of the Polybutadiene Polymer,Emulsifying Agent, and Nonionic Surfactant were added to a side mixtank. The contents were heated to 150° F. Under high shear mixingconditions, the indicated amount of hot deionized water was slowly addedto the side mix tank. During the water addition, the mixture invertedfrom a water-in-oil emulsion to an oil-in-water emulsion. For Example 7,Polybutadiene Polymer C was added under continuous stirring to a sidemix tank containing the indicated amounts of hot water and ammonia toform a clear solution that was added to the main mix tank. TheStyrene-butadiene Copolymer of Example 9 was supplied as an emulsionthat was directly added to the main mix tank.

For all examples, deionized water was added to the main mix tank and,while agitating, the specified amount of Silane was added. The Silanewas mixed until hydrolysis occurred (approximately 30 minutes). Thecontents of the side mix tank were then added to the main mix tank,while stirring. The main mix tank was then agitated while enoughdeionized water was added to bring the sizing composition to its desiredvolume.

Preparation of Fiber Glass Strands

Each of the sizing compositions in Tables 1-3 was applied to a fiberglass strand in the following manner. Fiber glass filaments, having anominal filament diameter of 16 microns were formed using a bushing andthen at least partially coated with one of the sizing compositions inTables 1-3 using a sizing applicator. The nominal loss on ignition ofthe fiber glass was 0.5 weight percent. The fiber glass filaments weregathered into a strand and then wound into a forming package on awinder. For Examples 1 and 2, each strand comprised 4,000 filaments witha nominal weight of 1984 tex. The strands were dried using dielectricdrying. For Examples 3-15, each strand comprised 1,200 filaments with anominal weight of 600 tex. The strands were dried at 40° C.

Measurement of Mechanical Properties for Examples 1 and 2

Two types of glass fibers were used: Sample 1, at least partially coatedwith sizing composition Example 1 from Table 1 and which is compatiblewith pDCPD resin and Comparative Example A, at least partially coatedwith PPG's commercial 1383 binder and which is compatible with epoxyresin. The nominal loss on ignition of the fiber glass was 0.55 weightpercent. Both types of glass were prepared as rovings (direct draw) fromfibers having a nominal filament diameter of 16 microns that had anominal weight of 1984 tex. The rovings were dried using dielectricdrying. A plurality of the rovings were woven into a plain woven fabricwith an areal density of 827 g/m². The matrix materials used were apDCPD formulation (indicated below as F2.06), supplied by Telene SAS,and a standard epoxy resin (Epikote 828 LVEL with Dyteck DCH 99hardener).

Unidirectional (UD) samples for bending tests were produced by means ofa hand pultrusion process by pulling impregnated fiber bundles through amold. Woven fabric laminates were produced by vacuum infusion of 4layers of glass fiber weave with the F2.06 pDCPD resin and also with theepoxy resin. The composite fiber volume fractions for the differenttypes of samples are in Table 4.

TABLE 4 pDCPD F2.06 - Epoxy - pDCPD F2.06 - Comparative ComparativeSample 1 Example A Example A Transverse 3 pb 0.59 0.61 0.56 samplesWoven laminates 0.53 / 0.56Adhesion Assessment with Three Point Bending Test

Transverse three point bending (3pb) tests on unidirectional sampleswere done according to the ISO 14125 standard to provide an indicationof the quality of the bond between fibers and matrix, for threecombinations of fiber sizing/matrix: the Sample 1 glass combined withthe F2.06 pDCPD matrix, and the Comparative Example A glass, combinedwith the epoxy matrix, as well as with the F2.06 pDCPD resin. Acrosshead displacement rate of 1 mm/min was used.

To investigate the quality of the fiber-matrix adhesion of the pDCPDF2.06/Sample 1 glass combination as compared to the epoxy/ComparativeExample A glass combination, which is known to have sufficient adhesion,a series of transverse three point bending tests was done onunidirectional samples. For completion, this was also done on pDCPDF2.06/Comparative Example A composites. Visual inspection of the lattersamples suggested poor impregnation quality, but they were still testedfor completeness.

Table 5 shows the average obtained transverse three-point bendingstrength for the three materials. The obtained strength for all threematerials was significantly different. The highest values were obtainedfor the F2.06/Sample 1 combination, followed by the EP/ComparativeExample A combination. Since the latter is known to have good adhesion,adhesion between fibres and matrix in the pDCPD F2.06/T73 material cantherefore be considered to be also very good.

TABLE 5 Three point bending strength Material Matrix Glass fibre type(MPa) F2.06/Sample 1 pDCPD Sample 1 (pDCPD 102 ± 14 F2.06 compatible)F2.06/Comparative pDCPD Comp. Example A 19 ± 7 Example A F2.06 (epoxycompatible) EP/Comparative Epikote 828 Comp. Example A 81 ± 7 Example ALVEL (epoxy compatible)Tensile Tests

Samples cut from the woven fabric laminates by water-cooled diamond saw,were used for static and fatigue tensile tests according to the ASTMD3039 and D3479 standards. Strain measurements during the static testswere done by means of digital image correlation. A test speed of 2mm/min was used. Fatigue tests were done in load-controlled mode on a160 kN hydraulic Schenck. The fatigue frequency was 5 Hz, and theR-ratio was 0.1. The chord modulus was determined as the ratio of thedifference in load over the difference in displacement for each cycle.

TABLE 6 Tensile strength Tensile modulus Failure strain Material (MPa)(GPa) (%) pDCPD F2.06/ 516 ± 14 23 ± 2 2.7 ± 0.1 Sample 1Epoxy/Comparative 502 ± 33 26 ± 3 2.9 ± 0.1 Example A

The results from the tensile tests on the woven fabric composite samplesare shown in Table 6. Final failure was in the gauge section for alltested samples. No significant difference between the two materials wasmeasured in terms of stiffness or strength. The failure strain for theepoxy samples was found to be marginally larger than that of the pDCPDcomposite. This may be explained by the pronounced loss in stiffness ofthe epoxy samples near the end of the test, caused by the build-up ofextensive delamination damage.

Pictures taken during the test with transmitted light do reveal amarkedly different damage development. FIG. 1 shows transmitted lightpictures taken during the tensile tests for different percentages ofstrain for both materials. The pDCPD composite does not show much damageup to around 1% of strain, after which a limited amount of short,localized transverse and longitudinal cracks start to develop. The firstsigns of the onset of delamination are in the second to last picture,which was taken approximately 1 second before failure (called JBF in thefigure). Final failure is very localized and consists of fiber failurewith a very limited amount of delamination. In the epoxy composites,however, after 0.5% of strain a multitude of transverse matrix crackscan already be seen. Not only are they more numerous, they are alsolonger and were seen to grow very quickly over the full width of thesample. The number of transverse cracks increases rapidly withincreasing strain. Between 1 and 2% of strain, longitudinal cracks werefound to develop. The first delaminations occur between 2 and 2.5% ofstrain and are localized on the ‘cross-over’ points of the fiber bundles(as may be expected in a woven fabric laminate). Many delaminations areformed, which grow and coalesce and finally cause final failure byextensive delamination and fiber failure.

Tensile fatigue tests were run at load levels of 250, 200 and 150 MPa.Since the tensile strength of both materials was approximately 500 MPa,this corresponds to 50, 40 and 30% of the tensile strength. At leastfive samples of each material were tested for each load level. Thefatigue life data are shown on the graph of FIG. 2. As opposed to thestatic tests, a relatively high percentage (about 65%) of fatiguesamples did not fail in the gauge area, but rather close to or in theend tabs. There was, however, no clear difference in fatigue lifebetween samples that failed at the tabs and samples that did not.

As shown in the data, no statistical significant difference in fatiguelife was found between the two materials, although the fatigue life datafor the pDCPD composite clearly seems to be situated in the higher endof the epoxy composite results range.

For all tested load levels, the variation in fatigue life for the pDCPDcomposite is much smaller than that for the epoxy composite. For acertain fatigue load level, the difference between the lowest andhighest observed fatigue life is about a factor ten for the epoxycomposite (i.e., one order of magnitude, which is in line with what iscommonly observed for epoxy composites), while for the pDCPD laminatethis difference is less than a factor three.

Because of these observations, for both materials the 95% confidenceinterval was determined. The 95% interval is also indicated on FIG. 2.The bottom dashed line of these intervals indicates the lower limit ofthe region containing with 95% confidence 95% of all future fatigue testresults for this material. Examination of these curves shows a veryclear difference between the two materials, as suggested already by theabove observations. This so-called 95/95 fatigue life is clearly muchhigher for the pDCPD composite than for the epoxy composite.

The graph in FIG. 3 shows the evolution of the chord modulus duringfatigue at 150 MPa (30% of the tensile strength). The chord modulus isthe ratio of (maximum load-minimum load)/(maximum position-minimumposition) for each cycle. The evolution of this modulus may be seen asrepresentative for the evolution in the stiffness of the sample duringfatigue. The graph indicates that the reduction in modulus for the epoxysamples is more pronounced than for the pDCPD samples.

This is supported by the observed evolution of damage in this type ofsamples during tensile fatigue as shown in FIG. 4. After 100 cycles,clear transverse cracks can already be seen in the epoxy composite. Atthis moment, only a very limited amount of short, localised cracks isfound in the pDCPD composite. As the number of cycles increases, shortlongitudinal cracks are also created. After around 1,000 cycles, theonset of local delamination from the cracks is observed for the epoxycomposite, while in the pDCPD composite there is no sign ofdelaminations at that time. At 10,000 cycles, starting delaminations arealso observed in the pDCPD composite. As the number of cycles increases,extensive areas of delaminations are formed in the epoxy composite,while the progression of this type of damage seems to be much slower inthe pDCPD composite. This explains the smaller decrease in the chordmodulus observed for the latter material. The overall damage evolutionin the two materials is in general very similar to that during a statictensile test, although there does seem to be a slightly higher degree of(localised) delamination in the pDCPD composite during fatigue thanduring static testing.

Drop Weight Impact Tests

Drop weight impact tests were done on 10×10 cm² samples cut from thewoven laminates with a semi-hemispherical impacter with a diameter of 16mm and a weight of 3.120 kg. The drop height was 49 cm and 81.5 cm,i.e., a potential impact energy of 15 and 25 joules, respectively.Assessment of the impact damage was done by means of visual inspectionwith the aid of transmitted light, as well as by ultrasonic C-scan.

Drop weight impact tests were performed on the pDCPD F2.06/Sample 1 andepoxy/Comparative Example A laminates with impact energies of 15 and 25joules. Due to the transparent nature of the samples, visual inspectionof the impact damage was possible. An example of a transmitted lightphotograph of two specimens impacted with an energy of 25 J is shown inFIG. 5. For both energy levels, this inspection clearly showed that thedamage in the epoxy laminates is more severe than that in the pDCPDlaminates. A central delaminated region with a very limited amount offibre damage is visible on the impact site. In the epoxy samples thisregion is surrounded by matrix cracks. These are not distinguishable inthe pDCPD laminate, although a slightly more opaque region around thedelaminated area in these samples seems to suggest the presence ofeither micro-cracks or fibre/matrix debonding.

C-scan ultrasonic imaging was used to determine the size of thedelaminations in the impacted samples. Since this is a transmission typeof scan, the result of the scan is not the sum of all delaminationsurfaces present in the material, but rather the projected surface ofall superposed delaminations. The results of the scans for both impactenergy levels of the two materials are shown in FIG. 6.

All the obtained data from the impact tests indicate a significantdifference in delamination size between the pDCPD and the epoxylaminates for equal impact energy. For both impact energy levels tested,the measured delamination size is found to be about two times larger forthe epoxy laminate than for the pDCPD laminate, indicating a tougherbehavior of the pDCPD composite.

Measurement of Mechanical Properties for Examples from Tables 2 and 3

The interlaminal shear strength (ILSS), flexural strength, and/orflexural modulus of the sized fiber glass strands were measured. Theinterlaminal shear strength was measured using the ISO 14130 testmethod. The flexural strength was measured using the. The flexuralmodulus was measured using the ISO 3597 test method. Table 7 providesthe results.

TABLE 7 Mean Flexural Number of Mean ILSS Mean Flexural ModulusComposition Measurements (MPa) Strength (MPa) (GPa)  3 2 17.7 561 28.8 4 2 17.7 565 27.3  5* 2 46.7 699 34.7  5* 2 44.3 861 34.5  6 2 21.8 66030.0   8** 2 39.9 822 32.0   8** 2 39.9 924 32.2  7 2 35.6 751 31.8  9 244.4 861 31.6 13 4 22.7 — — 11 4 28.6 — — 12 4 34.8 — — 15 6 37.1 — — 104 43.5 — — 14 6 43.2 — — *Compositions contain the same components butthe formulations were separately prepared. **Compositions contain thesame components but the formulations were separately prepared.

Desirable characteristics, which can be exhibited by the presentinvention, include, but are not limited to the provision of: sizingcompositions which are suitable for fiber glass that may be used toreinforce cycloolefinic resins cured by ROMP catalysts; sizingcompositions which are suitable for fiber glass to reinforce DCPD resinscured by ROMP catalysts; sizing compositions that can potentiallyparticipate in the polymerization and cross-linking mechanism of theDCPD resin; sizing compositions that utilize ingredients having a lowpotential to deactivate the ROMP catalyst; fiber glass that is effectivereinforcement for cycloolefinic resins that cure by the ROMP reaction;fiber glass that is effective reinforcement for DCPD resins that cure bythe ROMP reaction; DCPD composites having desirable shear strengths;DCPD composites having SBS values that substantially approach the SBSvalue of un-reinforced cured DCPD resin; and a cost-competitive, lowviscosity resin system (e.g., a resin system developed from DCPDmonomer) that cures without styrene co-monomer/diluent.

Various embodiments of the invention have been described in fulfillmentof the various objects of the invention. It should be recognized thatthese embodiments are merely illustrative of the principles of thepresent invention. Numerous modifications and adaptations thereof willbe readily apparent to those skilled in the art without departing fromthe spirit and scope of the present invention.

That which is claimed:
 1. A sizing composition for glass fibers,comprising: a film-former comprising a polymer, wherein each repeatingunit of the polymer comprises at least four carbon atoms and at leastone carbon-carbon double bond, the double bond being in the backbonechain of the polymer; and a silane, wherein the polymer comprisespolybutadiene and wherein the sizing composition comprises at leastabout 60 weight percent polybutadiene and more than 5 weight percentsilane on a total solids basis, and wherein one or more of the repeatingunits in the polymer comprises at least one pendant group.
 2. The sizingcomposition of claim 1, wherein the repeating unit of the polymercomprises up to six carbon atoms.
 3. The sizing composition of claim 1,wherein the at least one pendant group comprises at least one vinylgroup.
 4. The sizing composition of claim 1, wherein the at least onegroup comprises at least one cyclic pendant group.
 5. The sizingcomposition of claim 1, wherein one or more of the repeating units inthe polybutadiene comprises at least one pendant group.
 6. The sizingcomposition of claim 1, wherein the sizing composition comprises atleast about 70 weight percent polybutadiene on a total solids basis. 7.The sizing composition of claim 1, wherein the polybutadiene has anumber average molecular mass of less than 20,000.
 8. The sizingcomposition of claim 1, wherein the polybutadiene has a number averagemolecular mass of less than 10,000.
 9. The sizing composition of claim1, wherein the film-former comprises at least about 70 weight percent ofthe sizing composition on a total solids basis.
 10. The sizingcomposition of claim 1, wherein a first film-former comprises at leastabout 20 weight percent of the sizing composition on a total solidsbasis.
 11. The sizing composition of claim 10, further comprising asecond film-former.
 12. The sizing composition of claim 11, wherein thesecond film-former comprises at least about 20 weight percent on a totalsolids basis.
 13. The sizing composition of claim 1, wherein the silanecomprises a terminal vinyl group.
 14. The sizing composition of claim 1,wherein the silane comprises a vinylbenzyl group.
 15. The sizingcomposition of claim 1, wherein the silane comprises avinyltrialkoxysilane.
 16. The sizing composition of claim 1, wherein thesilane comprises a methacryloxypropyltrialkoxysilane.
 17. The sizingcomposition of claim 1, wherein the silane comprises between about 5andabout 20 weight percent of the sizing composition on a total solidsbasis.
 18. The sizing composition of claim 1, wherein the silanecomprises between about 10 and about 20 weight percent of the sizingcomposition on a total solids basis.
 19. A sizing composition for glassfibers, comprising: a film-former comprising a polymer, wherein eachrepeating unit of the polymer comprises at least four carbon atoms andat least one carbon-carbon double bond, the double bond being in thebackbone chain of the polymer; and a silane, wherein the polymercomprises polybutadiene and wherein the sizing composition comprises atleast about 60 weight percent polybutadiene and more than 5 weightpercent silane on a total solids basis, and wherein one or more of therepeating units in the polybutadiene comprises at least one pendantgroup.
 20. A sizing composition for glass fibers, comprising: afilm-former comprising a polymer, wherein each repeating unit of thepolymer comprises at least four carbon atoms and at least onecarbon-carbon double bond, the double bond being in the backbone chainof the polymer; and a silane, wherein the polymer comprisespolybutadiene and wherein the sizing composition comprises at leastabout 60 weight percent polybutadiene and more than 5 weight percentsilane on a total solids basis, and wherein the silane comprises avinylbenzyl group.
 21. A fiber glass strand comprising at least oneglass fiber at least partially coated with the sizing composition ofclaim
 1. 22. A polyolefin composite, comprising: (a) a plurality ofglass fibers at least partially coated with the sizing composition ofclaim 1; and (b) a poly olefin prepared by polymerizing a cycloolefinusing a ring-opening metathesis polymerization catalyst.
 23. Thepolyolefin composite of claim 22, wherein the polyolefin comprisespolymers formed by polymerizing dicyclopentadiene.